Spherical or spherical-like cathode material for a lithium battery, a battery and preparation method and application thereof

ABSTRACT

The present invention discloses a spherical or spherical-like lithium battery cathode material, a battery and preparation methods and applications thereof. The chemical formula of the cathode material is: Li a Ni x Co y Mn z M b O 2 , wherein 1.0≤a≤1.2; 0.0&lt;b≤0.05; 0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50; x+y+z+b=1; M is one or two or more of Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Ba and a rare earth element. A single α-NaFeO 2  type layered structure of the cathode material is shown by a powder X-ray diffraction pattern and full width at half maximum FWHM (110) of the (110) diffraction peak near a diffraction angle 2θ of 64.9° is in the range of 0.073 to 0.145; the morphology of the cathode material is spherical or spherical-like primary particles and a small amount of secondary particles; the cumulative percentage of the number of particles having a particle diameter of 5 μm or less is usually larger than 60% in the number-basis particle sizes of primary particles and secondary particles agglomerated by primary particles of the cathode material. The cathode material in the present invention has excellent circulating performance, storage performance and safety performance under high temperature and high voltage, and is suitable for digital product, electric vehicle, electric bicycle, fast charging bus, passenger car, communication product, electric power and energy storage system etc.

RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.15/602,311, filed May 23, 2017, which claims priority to CN201611168653.6, filed Dec. 16, 2016. The contents of each of theseapplications are incorporated herein by reference.

FIELD OF THE INVENTION

The invention belongs to a technical field of lithium ion battery, andrelates to a lithium ion battery cathode material of a spherical orspherical-like layered structure, preparation methods thereof and asecondary lithium ion battery made of the cathode material.

BACKGROUND OF THE INVENTION

Nickel-cobalt-manganese (NCM) ternary materials have advantages of highspecific capacity, low cost and good thermal stability etc., therefore,they have a very broad application prospect in the field of energystorage and electric vehicle. However, poor cycling performance is animportant factor affecting the application of NCM ternary materials fora long time. The main transition elements are Ni, Co and Mn in NCMternary materials, in which NCM ternary materials with differentproperties can be obtained with different ratios of the three elements.When contacting with an electrolytic solution, the stability of thematerial also changes due to the different ratios of elements. Thefactors affecting the cycle life of the ternary materials are: 1.Reconstruction of the surface crystal structure during the cyclingprocess; 2. Secondary particles rupture due to the volume expansion ofthe anisotropy during the cycling process. It was found that theconnecting structure between particle and particle in the secondaryparticles could cause localized current density to rise, which causedgreat stress and therefore affected the cycling performance of thematerial. At the same time, there was a phenomenon of inconsistency ofcharge state between various parts of particles, which would affect theelectrochemical performance of an electrode.

In addition, when the amount of lithium deintercalation is larger, thestructure of NCM ternary materials becomes very fragile, and adisplacement of active metal and oxygen occurs in the crystal lattice,and when under a certain high temperature and high pressure, atomicrearrangement gradually increases, volume and phase of crystalline grainchange largely. On the other hand, chemical and electrochemicalreactions of the ternary materials with the electrolyte cause thematerial easy to deoxidation and the transition metal dissolved,especially the electrolyte in the high-voltage will be oxidized toproduce H+ and the acidity of the electrolyte are improved. So a surfacefilm of the electrode material is damaged by HF, and a composition andstructure of the interface are further changed, seriously affecting theelectrochemical performance and cycling performance of the material.

In order to solve the above-mentioned problems, NCM ternary materialsare modified by bulk doping and surface coating modification, which isan effective method. The bulk doping of NCM ternary materials caneffectively restrain the structure change, enhance the reversibility ofmaterials and restrain the increase of the charge transfer impedanceduring the cycling process. The surface coating modification of NCMternary materials can effectively avoid direct contact of the materialswith the electrolyte, especially with HF in the electrolyte, thusprevent the occurrence of side reactions, inhibit crystal phase changesof the materials, thereby improve cycling stability and multiplicationof the materials etc.

It was reported in Chinese invention patent of Application No.200780013946.X, Publication No. CN101427403A, entitled “PositiveElectrode Active Material Powder” that, the positive electrode activematerial powder of this invention comprised primary particles andaggregated particles by primary particles, and the average particlediameter on volume basis of the primary particles and the aggregatedparticles by the primary particles is 0.1 μm to 3 μm, and the percentageof the sum of the volume of particles having a particle diameter of 5 μmor more to the sum of the volume of all the particles is below 10%, anda BET specific surface area of the powder is more than 2 m²/g and lessthan 7 m²/g. It was reported in Chinese invention patent of ApplicationNo. 200780013765.7, Publication No. CN101421867A, entitled “PositiveElectrode Powder and Cathode Mixture” that, the positive electrodepowder of this invention contains a positive electrode active materialpowder and a graphite powder, wherein the positive electrode activematerial powder contains primary particles and aggregated particles byprimary particles, and more than 90% of the particles have a particlediameter of 0.1 μm to 5 μm, and a BET specific surface area of thepowder is 1 m²/g to 7 m²/g. It was reported in Chinese invention patentof Application No. 200780004424.3, Publication No. CN101379637A,entitled “A lithium transition metal compound powder of cathode materialfor lithium secondary battery and preparation methods thereof, aspray-dried body and calcined precursor thereof, a positive electrodefor a lithium secondary battery and a lithium secondary battery usingthe lithium transition metal compound powder” that, thelithium-nickel-manganese-cobalt based composite oxide powder of cathodematerial for lithium secondary battery in this patent has a half widthof the (110) diffraction peak in the vicinity of a diffraction angle 2θof 64.5° of between 0.01 and 0.2 in the powder X-ray diffraction.

SUMMARY OF THE INVENTION

Aiming at the defect in the prior art that the cathode materialstructure is prone to fragmentation, which can cause contact of thematerial with the electrolytic solution to cause a side reaction toaffect the cycling performance of the battery, the present inventionaims to provide lithium ion battery cathode material of a spherical orspherical-like layered structure, and the material has an integritystructure, a good processing performance, without cases of particlefragmentation in the cycling process, effectively prevent direct contactof the surface of material with the electrolytic solution, especiallycontact with HF in the electrolytic solution, thus prevent occurrence ofside reactions, stabilize the crystal structure of the material, and caneffectively improve the battery cycling performance under hightemperature and high voltage, especially stability under hightemperature and safety performance when applied to the lithium-ionbattery, especially the power lithium-ion battery.

Specifically, the present invention provides a lithium ion batterycathode material of a spherical or spherical-like layered structure,wherein the cathode material has a chemical formula:

Li_(a)Ni_(x)Co_(y)Mn_(z)M_(b)O₂, wherein 1.0≤A≤1.2; 0.0<b≤0.05;0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50; x+y+z+b=1; and M is one or moreof Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Ba and a rare earth element.

Preferably, the cathode material powder comprises primary particles of amorphology of spherical or spherical-like shape and a small amount ofsecondary particles agglomerated by primary particles under scanningelectron microscope (SEM), wherein cumulative percentage of the numberof particles having a particle diameter of 5 μm or less is generallygreater than 60% in the number-basis sizes of primary particles andsecondary particles agglomerated by primary particles of the cathodematerial.

In the present invention, the particle size of the cathode materialpowder is determined by the particle size distribution of the laserdiffraction scattering method, and the cumulative distribution isobtained by the frequency distribution accumulation.

Preferably, a doping amount b of the doping element M is 0.001 to 0.5,and also preferably 0.002 to 0.03.

Preferably, a single α-NaFeO₂ type layered structure of the cathodematerial is shown by the powder X-ray diffraction spectrum (XRD).

Preferably, full width at half maximum FWHM (110) of the (110)diffraction peak near a diffraction angel 2θ of 64.9° is 0.073 to 0.145in the powder X-ray diffraction spectrum (XRD) of the cathode material.

Preferably, the lithium ion battery cathode material of a spherical orspherical-like layered structure is characterized in that a specificsurface area measured by BET method is 0.3 to 0.9 m²/g.

Preferably, the lithium ion battery cathode material of a spherical orspherical-like layered structure is characterized in that a medianparticle diameter of the cathode material is 3.0 to 8.0 μm, preferably aparticle median diameter of 4.0 to 7.0 μm.

The present invention also aims to provide a preparation method for alithium-nickel-cobalt-manganese-oxygen cathode material of a sphericalor spherical-like layered structure, comprising at least the followingsteps:

mixing a lithium source, a M source and a nickel-cobalt-manganeseprecursor in a following molar ratio of Li, M and (Ni+Co+Mn),respectively a is 1.0 to 1.2, 0.0<b≤0.05, Ni+Co+Mn is 0.95 to 1.0, andsintering the obtained mixture at 800 to 1000° C. (preferably sinteringthe mixture for 4 to 30 hours), and cooling, and pulverizing andclassifying to obtain a lithium ion battery cathode material of aspherical or spherical-like layered structure.

The present invention also aims to provide a preparation method for alithium-nickel-cobalt-manganese-oxygen cathode material of a sphericalor spherical-like layered structure, comprising at least the followingsteps:

dispersing a lithium source into a polyethylene glycol or an acrylamideaqueous colloid to prepare a colloid, and adding nickel-cobalt-manganeseprecursor according to a molar ratio ofLi:(Ni+Co+Mn)=(1.0-1.2):(0.95-1.0) into the colloid to obtain a mixedmaterial, and pre-sintering the mixed material at 400 to 800° C. andthen sintering at 800 to 980° C., and cooling, and pre-pulverizing andclassifying to obtain a lithium-nickel-cobalt-manganese-oxygen cathodematerial intermediate A, adding a solution of M source or a dispersion Binto A to obtain a mixture C, and post-sintering the mixture C at 500 to960° C., and cooling, and pulverizing and classifying to obtain alithium ion battery cathode material of a spherical or spherical-likelayered structure.

Preferably, wherein, said pre-sintering is carried out for 4 to 8 hours,and said sintering is carried out for 8 to 20 hours, and saidpost-sintering is carried out for 4 to 10 hours.

Preferably, wherein, a pressure of said pre-pulverizing is 0.1 to 1.0MPa, preferably 0.3 to 0.4 MPa, and a pressure of said pulverizing is0.1 to 0.8 MPa, preferably 0.4 to 0.7 MPa.

Preferably, the above-mentioned preparation method of the cathodematerial is characterized in that a median particle diameter D50 of thenickel-cobalt-manganese precursor is 3 to 12 μm, preferably 4 to 10 μm.

Preferably, the above-mentioned preparation method of the cathodematerial, wherein the lithium source used is one or two or more mixtureof lithium carbonate, lithium hydroxide monohydrate, lithium nitrate andlithium acetate.

Preferably, the above-mentioned preparation method of the cathodematerial, wherein, the preparation method of the cathode material ischaracterized in that the nickel-cobalt-manganese precursor used is oneor more of the group consisting of nickel-cobalt-manganese hydroxide,nickel-cobalt-manganese carboxyl oxide, and nickel-cobalt-manganeseoxide.

Preferably, a method of adding the M source includes, but is not limitedto, one or two or more of mechanical mixing, co-precipitation, andemulsification etc.

Preferably, the M source is an oxide of one or two or more selected fromthe group consisting of Mg, Al, Ti, Zr, Y, Co, Ni, Mn, Ba and a rareearth element, or a salt thereof or an organic compound thereof, andincludes but is not limited to, acetic acid salt, sulfate, hydroxylcompound or ester compound etc., preferably ester compound, morepreferably selected from tetrabutyl zirconate, or a mixture of cobalthydroxide and nickel hydroxide.

The present invention also provides a lithium ion battery, which ischaracterized by comprising at least one of the cathode material of thepresent invention or the cathode material obtained by the preparationmethod of the present invention as a positive electrode active material.

Wherein, preferably, a circulation capacity retention ratio of thelithium ion battery is more than 90%.

The present invention also provides a lithium ion battery cathodematerial obtained by any one of the preceding preparation methods.

Wherein, when the cathode material of the present invention as apositive electrode active material is used for preparing a positiveelectrode of lithium ion battery, the positive electrode of the batterycontains less than or equal to 10% by weight, preferably less than orequal to 8% by weight, more preferably 3 to 5% by weight of conductivecarbon black, in addition to the positive electrode active material.

The present invention also provides a communication, an electric power,an energy storage system or a mobile storage device, which ischaracterized in that it is prepared by using the lithium ion batterydescribed above.

The present invention also provides a use of a lithium ion battery as apower source for communication, power or energy storage system, mobilestorage device, or electric vehicle.

The present invention also provides a use of the lithium ion battery ina mobile digital product (3C), an electric vehicle (xEV), an electricbicycle, a fast charge bus or a passenger car.

A cobalt-nickel-manganese precursor, a M-source and a lithium source aremixed, sintered and pulverized to prepare a cathode material by thepresent invention. A single α-NaFeO₂ type layered structure of thecathode material is shown by the powder X-ray diffraction spectrum (XRD)and full width at half maximum FWHM (110) of the (110) diffraction peaknear the diffraction angle 2θ of 64.9° is generally 0.073 to 0.145. Themorphology of the cathode material is shown as primary particle ofspherical or spherical-like shape and a small amount of secondaryparticles agglomerated by primary particles under the scanning electronmicroscope (SEM). The cumulative percentage of the number of particleshaving a particle diameter of 5 μm or less is generally larger than 60%in the number-basis sizes of primary particles and secondary particlesagglomerated by primary particles of the cathode material; thecumulative percentage of the volume of particles having a particlediameter of 5 μm or less is generally greater than 25% in the volumesizes of primary particles and secondary particles agglomerated byprimary particles of the cathode material.

The cathode material provided by the present invention has excellentcycling performance, storage performance and safety performance underhigh temperature and high voltage, and is suitable for digital product,electric vehicle, electric bicycle, fast charge bus, passenger car,communication, electric power and energy storage system etc.

Compared with nickel-cobalt-manganese ternary cathode materials mainlybased on the secondary aggregated particles, the lithium ion batterycathode material of spherical or spherical-like layered structure mainlybased on primary particles of the present invention can effectivelyavoid the occurrence of secondary aggregated particle fragmentation, thecathode material has excellent cycling performance and safetyperformance under high temperature and high voltage, and is suitable fordigital product, electric vehicle, electric bicycle, fast charging bus,passenger cars, communication, electricity, energy storage systems etc.

The preparation method of the present invention is simple, thepreparation process is easy to control and operate, and the productioncost is low.

DESCRIPTION OF DRAWINGS

FIG. 1A is a powder X-ray diffraction pattern (XRD) of the lithium ionbattery cathode material D1 of a spherical or spherical-like layeredstructure prepared in Example 1;

FIG. 1B is a scanning electron micrograph (SEM) of the lithium ionbattery cathode material D1 of a spherical or spherical-like layeredstructure prepared in Example 1;

FIG. 2 is a scanning electron micrograph (SEM) of the lithium-ionbattery cathode material D2 of a spherical or spherical-like layeredstructure prepared in Example 2;

FIG. 3 is a scanning electron microscope (SEM) of the lithium ionbattery cathode material D3 of a spherical or spherical-like layeredstructure prepared in Example 3;

FIG. 4 is a powder X-ray diffraction pattern (XRD) of the lithium ionbattery cathode material D4 of a spherical or spherical-like layeredstructure prepared in Example 4;

FIG. 5A is a powder X-ray diffraction pattern (XRD) of ComparativeExample 1;

FIG. 5B is a scanning electron micrograph (SEM) of Comparative Example1;

FIG. 6A is a powder X-ray diffraction pattern (XRD) of ComparativeExample 2;

FIG. 6B is a scanning electron micrograph (SEM) of Comparative Example2;

FIG. 7 is a comparison chart of all Examples and Comparative Examples at4.2 V, 45 C, 1.0 C/1.0° C. after 500 cycles.

FIG. 8 is a comparison chart of all Examples and Comparative Examples at4.4 V, 45 C, 1.0° C./1.0 C after 200 cycles.

EMBODIMENT

The present invention will now be described in more detail by way ofspecific examples, with reference to the accompanying drawings.

A preparation method of a lithium ion battery cathode material of aspherical or spherical-like layered structure of the present inventionis prepared by one of two methods comprising the following steps:

Method 1: mixing a lithium source, a M source and anickel-cobalt-manganese precursor (D50: 3-12 μm) according to a molarratio of Li:M:(Ni+Co+Mn)=(1.0-1.2):(0-0.05, but not includes 0):(0.95 to1.0), and heating the mixture from room temperature at a heating rate of15.0 to 25.0° C./min, and sintering at 800 to 1000° C. for 4 to 30hours, and cooling, and pulverizing and classifying to obtain a lithiumion battery cathode material of a spherical or spherical-like layeredstructure.

Method 2: dispersing a lithium source into a polyethylene glycol or anacrylamide aqueous colloid to make a colloid, then adding anickel-cobalt-manganese precursor according to a molar ratio ofLi:(Ni+Co+Mn)=(1.0-1.2):(0.95-1.0) to the colloid to obtain a mixture,and heating the mixture from room temperature at a heating rate of 15.0to 25.0° C./min, and pre-sintering at 400 to 800° C. for 4 to 8 hours,and heating the mixture at a heating rate of (15.0 to 25.0)° C./min andsintering at 800-980° C. for 8-20 hours, and cooling, andpre-pulverizing and classifying to obtain alithium-nickel-cobalt-manganese-oxygen cathode material intermediate A,and adding a solution of M source or a dispersion B into A to obtain amixture C, wherein compare to 1.0 to 1.2 molar of lithium source, theadding amount of M source is greater than zero and less than or equal to0.05 molar. Heating the mixture C at a heating rate of 15.0 to 25.0°C./min, and sintering at a temperature of 500 to 960° C. for 4 to 10hours, and cooling, and pulverizing and classifying to obtain a lithiumion battery cathode material of a spherical or spherical-like layeredstructure.

Wherein, in the above-mentioned method 2, the mass concentration of thepolyethylene glycol or the acrylamide aqueous colloid used as rawmaterials when dispersing are preferably as follows: the massconcentration of polyethylene glycol in the polyethylene glycol aqueouscolloid is preferably 1 to 3%, the mass concentration of the acrylamideaqueous colloid is preferably 2 to 5%.

In a preferable embodiment of the present invention, the presentinvention also provides a lithium ion battery cathode material ofspherical or spherical-like layered structure, which is characterized inthat a chemical formula of the cathode material isLi_(a)Ni_(x)Co_(y)Mn_(z)M_(b)O₂, wherein 1.0≤a≤1.2; 0.0<b≤0.05;0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50; x+y+z+b=1; M is one or more ofMg, Ti, Al, Zr, Y, Co, Mn, Ni, Ba and a rare earth element.

Wherein, the cathode material powder comprises primary particles of amorphology of spherical or spherical-like and a small amount ofsecondary particles agglomerated by primary particles under scanningelectron microscope (SEM), wherein the cumulative percentage of thenumber of particles having a particle diameter of 5 μm or less isgenerally greater than 60% in the number-basis sizes of primaryparticles and secondary particles agglomerated by primary particles ofthe cathode material.

In the case where the cathode material of the present invention is usedfor preparing a positive electrode, a cathode material of the presentinvention used as a positive electrode active material is coated on apositive electrode current collector to prepare and obtain a positiveelectrode together with a conventional adhesive agent and a conventionalconductive additive and so on. For example, carbon black is preferred asa conventional conductive additive. For example, polyvinylidene fluoride(PVDF) is preferred as a conventional adhesive agent. The amount of thecarbon black added is usually not more than 10%, preferably not morethan 8%, more preferably between 3% and 5% of the total cathodematerial. However, the positive electrode active material powderrecorded in the Chinese Patent of Application No. 200780013765.7 andPublication No. CN101421867A is required to be disclosed in ChinesePatent Publication No. CN101421867A is required to be mixed with alarger amount of graphite powder (content: 5% to 20% by weight). What'smore, the discharge capacity of the positive electrode of the patentprepared by the powder used for positive electrode at 1 C is up to 143mAh/g (condition of 4.3-3.0 V), which is much smaller than the averagedischarge capacity in the present invention of about 160-175 mAh/g(condition of 4.35-3.0 V) (the average discharge capacity of the presentinvention is about 155-171 mAh/g under 4.3-3.0 V), and the capacitancevalue of the present invention can be up to 202 mAh/g. This may bemainly due to the fact that the cathode material prepared by the presentinvention has a stronger stability, a moderate specific surface area, acomplete material structure and a good processability, and does notcause particle fragmentation during the cycling process, and thus thebattery prepared by the cathode material of the present invention has anexcellent circulation capacity retention ratio.

The technical solution of the present invention will be described infurther detail with reference to specific examples.

EXAMPLE

The sintering equipment used in the examples: muffle furnace of YixingQianjin Furnace Industry Equipment Co., Ltd.

Pulverizing equipment: SHQM Type of Dual Planetary Ball Mill of Lianyungang Chunlong Experimental Instrument Co., Ltd; Airflow Pulverizing:MX-50 Airflow Pulverizer of Yixing Juneng Pulverizing Equipment Company.The pressure of airflow pulverizing in the following Examples 1-7 of thepresent invention is 0.1-1.0 MPa.

Analytical Instruments: MSU2000 Laser Particle Size Analyzer of BritishMalvern, SSA-3500 automatic specific surface analyzer produced and soldby Beijing Bi'ao Electronic Technology Co., Ltd; Supra55 sapphire fieldemission scanning electron microscope of Germany Zeiss, with amagnification of 5000 times by the microscope; X'pert PRU X-raydiffractometer of Netherlands Panne with a target of Cukα, a wavelengthof 1.54 Å, a test voltage of 40 kV, a test current of 40 mA and a stepof 0.013°; LIP-3AHB06 high temperature formation system of ZhejiangHangke; CT2001C Test Equipment of Wuhan LAND electronics; KP-BAK-03E-02efficient vacuum oven of Kerui Electrical, Dongguan City.

The secondary lithium ion battery of the present invention is composedof an electrode, a non-aqueous electrolyte, a separator and a container.Specifically, the electrode includes a positive electrode and a negativeelectrode, and the positive electrode is made of a material including apositive electrode current collector and a positive electrode activematerial coated on the positive electrode current collector with aconventional adhesive and a conventional conductive additive or thelike, and the positive electrode active material is the lithium ionbattery cathode material of primary spherical or spherical-like of thepresent invention. The negative electrode is made of a materialincluding collector and a conventional negative electrode activematerial coated on the collector with a conventional adhesive and aconventional conductive additive or the like. The separator is a PP/PEfilm conventionally used in the industry for separating the positive andnegative electrodes from each other; the container is a containingobject of a positive electrode, a negative electrode, a separator, andan electrolyte.

In the following examples, the specific method of manufacturing thesecondary lithium ion button cell with the lithium ion battery cathodematerial of spherical or spherical-like layered structure prepared bythe present invention is shown as follows:

Positive electrode preparation: the lithium ion battery cathode materialof spherical or spherical-like layered structure of the presentinvention, a conductive carbon black (SP) and an adhesive ofpolyvinylidene fluoride (PVDF) were added into N-Methylpyrrolidone (NMP)(a weight ratio of lithium-nickel-cobalt-manganese cathode material toNMP is 2.1:1) in a weight ratio of 90:5:5 and the mixture was mixedthoroughly, and stirred to form a uniform slurry, and coated on thealuminum foil collector, and dried and pressed into pole pieces. Thepressed positive pole piece was punched, weighed and baked, and then wasassembled into battery in a vacuum glove box. Put the bottom shell ofthe button cell firstly, and foamed nickel (2.5 mm) and negative lithiummetal sheet (produced by Tianjin, 99.9%) were put on the top of thebottom shell, 0.5 g electrolytic solution was injected in the conditionof relative humidity of less than 1.5% using a mixed solvent of EC, DEC,and DMC with a mass ratio of EC:DEC:DMC=1:1:1, the electrolyte was 1Mhexafluorophosphate, putted the separator and the positive electrode,and then covered the button cell cover and sealed the battery. The modelof the button cell is CR2430.

In the following examples, the method of preparing the secondary lithiumion battery by the lithium ion battery cathode material of the sphericalor spherical-like layered structure prepared by the present invention isshown as follows:

Positive cathode preparation: The lithium ion battery cathode materialof the spherical or spherical-like layered structure of the presentinvention, conductive carbon black (SP) and an adhesive ofpolyvinylidene fluoride (PVDF) were added into N-Methylpyrrolidone (NMP)(a weight ratio of lithium-nickel-cobalt-manganese cathode material toNMP is 2.1:1) in a weight ratio of 94:3:3, the mixture was mixedthoroughly, stirred to form a uniform slurry, coated on the aluminumfoil collector, dried and pressed to form an electrode.

Negative electrode preparation: negative artificial graphite, conductivecarbon black (S.P), carboxymethyl cellulose (CMC) and an adhesive (SBR)at a weight ratio of 95:1:1:3 were added into a sufficient amount ofpure water, and the mixture was mixed and stirred to form a uniformslurry, coated on a copper foil collector, dried and pressed to form anelectrode.

The separator is PP/PE composite film material. Lug was spotted weld tothe pressed positive and negative electrode, the separator was inserted,the materials were rolled in the winding machine and then put into thesoft package fixture, and then sealed the top and side of the softpackage., and then baked in the oven, and then 9 g of electrolyticsolution was injected in the condition of relative humidity of less than1.5% using a mixed solvent of DE, DEC, and DMC with a mass ratio ofEC:DEC:DMC=1:1:1, the electrolyte was 1M lithium hexafluorophosphate.After injection and formation for 48 hours, the soft package wasvacuumized and sealed. The battery model is 454261.

The charging and discharging test of the secondary lithium ionexperiment battery prepared by the present invention was tested on theWuhan LAND electronics battery tester according to the test method ofGB/T18287-2000.

Source of reagent used in the Examples is given as table A:

Reagent name Grade Model Manufacturer cobalt sulfate Industrial grade 98wt % Nanjing Chemical Reagent Factory heptahydrate nickel sulfateIndustrial grade 98 wt % Nanjing Chemical Reagent Factory hexahydratemanganese sulfate Industrial grade 98 wt % Nanjing Chemical ReagentFactory monohydrate zirconium nitrate Industrial grade 97 wt % NanjingChemical Reagent Factory pentahydrate yttrium nitrate Industrial grade95 wt % Nanjing Chemical Reagent Factory hexahydrate manganese acetatebattery grade 99.50% Dalian First Organic Chemical Co., Ltd cobaltacetate battery grade 99.50% Hubei Xingyinhe Chemical Raw Material Co,Ltd nickel acetate battery grade 99.50% Tongyuan Chemical Industrynickel-cobalt- Composite of — Guizhou Zhenhua E- manganese manganeseacetate, CHEM Co., Ltd carboxyl oxide cobalt acetate, and nickel acetatenano magnesium ceramic grade — Anhui Xuancheng Jingrui New oxideMaterial Co., Ltd nano yttrium oxide ceramic grade — Anhui XuanchengJingrui New Material Co., Ltd nano zirconium ceramic grade AnhuiXuancheng Jingrui New oxide Material Co., Ltd tungsten oxide ceramicgrade Anhui Xuancheng Jingrui New Material Co., Ltd tetra-n-butyltitanate reagent grade 99.80% Nanjing Chemical Reagent Factorytetrabutyl zirconate reagent grade 99.80% Nanjing Chemical ReagentFactory nano aluminium ceramic grade — Anhui Xuancheng Jingrui Newoxide(nano Al₂O₃) Material Co., Ltd lithium hydroxide battery grade 99.5wt % Jiangxi Ganfeng Lithium monohydrate Co., Ltd lithium carbonatebattery grade 99.5 wt % Jiangxi Ganfeng Lithium Co., Ltd lithium nitratebattery grade 99.5 wt % Shanghai Oujin Industrial Co., Ltd lithiumacetate battery grade 99.5 wt % Sichuan Guoli Lithium material Co., Ltdhigh purity oxygen industrial grade 99.95% pure Shenzhen Nanshan gasstation conductive carbon battery grade Super P Li Swiss TIMCAL Companyblack N-methyl- battery grade 99.5% of Jiangsu Nanjing Jinlongpyrrolidone content Chemical Plant polyvinylidene battery grade Solef6020 Solvaychemical company difluoride of America aluminium foil batterygrade 16 μm thick Alcoa Inc., AA electronic tape electronic grade agreen width of 3M Company of America 10 mm lithium sheet electronicgrade a diameter Φof Shanghai Shunyou Metal 20 mm, Material Co., Ltdpurity ≥99.9% electrolytic electronic grade LIB301, Shenzhen CapchemCompany solution propylene carbonate (PC): ethylene catbonate(EC):diethyl catbonate(DEC) = 1:1:1(volume ratio), concentration of lithiumsalt LiPF6: 1 mol/L seperator — three layer Celgard Company of Americamaterial of PP/PE/PP, Celgard M825, thickness of 16 μm aluminum filmindustrial grade a total thickness DNP Company of Japan of 160 μm

Example 1

1.04 mol of lithium hydroxide monohydrate was dispersed into 600 ml ofacrylamide aqueous colloid having a mass concentration of 5%, themixture was made to be a colloid at a rotation speed of 55 rpm for 90min, and the carboxyl oxide (D50: 3 μm) of nickel-cobalt-manganeseprecursor having a molar ratio of Ni:Co:Mn=5:2:3 was added to thecolloid at a molar ratio of Li:(Ni+Co+Mn)=1.04:0.998, and a mixedmaterial was obtained at a rotation speed of 2000 rpm for 30 minutes,and the mixed material was put in a muffle furnace and heated at a rateof 15° C./min to 800° C. to be pre-sintered for 4 hours in an airatmosphere, and cooled to room temperature, then heated at a rate of 17°C./min to 980° C. to be sintered for 8 hours in an air atmosphere, andcooled to room temperature, then air pre-pulverized in an air pressureof 1.0 Mpa to get a cathode material intermediate A oflithium-nickel-cobalt-manganese-oxygen for stand-by. 0.002 mol oftetrabutyl titanate was added to 0.2 mol of isopropanol and the mixturewas stirred for 10 min to obtain a solution B containing elementtitanium for stand-by. The organic solution B was added to the cathodematerial intermediate A of lithium-nickel-cobalt-manganese and themixture was stirred for 30 min to obtain a mixture C. The mixture C wasput in a muffle furnace and heated in an air atmosphere at a heatingrate of 15° C./min to 960° C. to be sintered (Hereinafter referred to as“post-sintering”, the following experiments are the same) for 4 hours,and cooled to room temperature, and air pulverized at a pressure of 0.7MPa, and classified by a 300-mesh metal mesh to obtain a lithium ionbattery cathode material D1 of spherical or spherical-like layeredstructure.

The cathode material D1 powder was measured by the X-ray diffractionpattern, as shown in FIG. 1a . The test results showed that full widthat half maximum FWHM (110) of the (110) diffraction peak at diffractionangle 2θ of 64.92 was 0.073, and the structure of the cathode materialwas a single α-NaFeO₂ type layered structure.

The cathode material D1 powder was subjected to a scanning electronmicroscope test, as shown in FIG. 1B. The cathode material D1 powdermainly included the primary particles of a morphology of spherical orspherical-like and a small amount of secondary particles agglomerated byprimary particles.

The cathode material D1 powder was subjected to particle size andspecific surface area tests, the D50 was 3.0 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 94.4%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 63.5%, and theBET specific surface was 0.90 m²/g.

Specifically, the corresponding conditions (sintering temperature,sintering time, airflow pulverizing pressure, M source and product) inthe sintering step of the cathode material D1 are summarized in Table 1,as shown in Table 1. The index data of the cathode material D1 (thediffraction angle of the (110) plane of the X-ray diffraction, thehalf-width of the crystal plane, the cumulative percentages of numberand the volume basis of the particle size of 5 μm or less; D50 and BET)are summarized in Table 2. The test results of the battery performancepreparing by powder D1 as the active material of the cathode materialare shown in Table 3.

Example 2

1.0 mol of lithium hydroxide monohydrate was dispersed into 650 ml ofpolyethylene glycol aqueous colloid having a mass concentration of 2%,the mixture was made to be a colloid at a rotation speed of 80 rpm for75 min, and the hydroxide (D50: 4 μm) of nickel-cobalt-manganeseprecursor having a molar ratio of Ni:Co:Mn=6:2:2 was added to thecolloid at a molar ratio of Li:(Ni+Co+Mn)=1.0:0.95, and a mixed materialwas obtained at a rotation speed of 2400 rpm for 40 minutes, and themixed material was put in a muffle furnace and heated at a rate of 18°C./min to 650° C. to be sintered for 5 hours in an oxygen atmosphere,cooled to room temperature, then heated at a rate of 19° C./min to 930°C. to be sintered for 12 hours in an oxygen atmosphere, and cooled toroom temperature, and air pre-pulverized in an air pressure of 0.5 Mpato get a cathode material intermediate A oflithium-nickel-cobalt-manganese-oxygen for stand-by. 0.03 mol of cobaltacetate and 0.02 mol of manganese acetate were added to pure water andthe mixture was stirred for 15 min to obtain a solution B containingelement cobalt and manganese for stand-by. The solution B was added tothe cathode material intermediate A oflithium-nickel-cobalt-manganese-oxygen and the mixture was stirred for40 min to obtain a mixture C. The mixture C was put in a muffle furnaceand heated in an oxygen atmosphere at a heating rate of 18° C./min to910° C. to be sintered for 5 hours, and cooled to room temperature, andair pulverized at a pressure of 0.5 MPa, and classified by a 300-meshmetal mesh to obtain a lithium ion battery cathode material D2 ofspherical or spherical-like layered structure.

The cathode material D2 powder was tested by the X-ray diffractionpattern, and the test results showed that full width at half maximumFWHM (110) of the (110) diffraction peak at diffraction angle 2θ of64.89 was 0.120, and the structure of the cathode material was a singleα-NaFeO₂ type layered structure.

The cathode material D2 powder was subjected to a scanning electronmicroscope test, as shown in FIG. 2. The cathode material D2 powdermainly included the primary particles of morphology of spherical orspherical-like and a small amount of secondary particles agglomerated byprimary particles.

The cathode material D2 powder was subjected to particle size andspecific surface area tests, the D50 was 3.4 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 91.2%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 62.3%, and theBET specific surface was 0.78 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material D2 are summarized in Table 1, as shown inTable 1. The index data of the cathode material D2 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2. The test results of the battery performance preparing by powderD2 as the active material of the cathode material are shown in Table 3.

Example 3

Lithium carbonate, magnesium acetate, yttrium oxide and oxide (D50: 7.5μm) of nickel-cobalt-manganese precursor having a molar ratio ofNi:Co:Mn=5:2:3 were mixed uniformly at a molar ratio ofLi:Mg:Y:(Ni+Co+Mn)=1.2:0.001:0.005:0.994 at a rotation speed of 300 rpmfor ball-milling for 50 minutes, and the mixture was put in a mufflefurnace and heated at a rate of 18° C./min to 800° C. to be sintered for30 hours in an air atmosphere, and cooled to room temperature, and airpre-pulverized and classified by a 300-mesh metal mesh to get lithiumion battery cathode material D3 of spherical or spherical-like layeredstructure.

The cathode material D3 powder was tested by the X-ray diffractionpattern, and the test results showed that full width at half maximumFWHM (110) of the (110) diffraction peak at diffraction angle 2θ of64.90 was 0.098, and the structure of the cathode material was a singleα-NaFeO₂ type layered structure.

The cathode material D3 powder was subjected to a scanning electronmicroscope test, as shown in FIG. 3. The cathode material D3 powdermainly included the primary particles of a morphology of spherical orspherical-like and a small amount of secondary particles agglomerated byprimary particles.

The cathode material D3 powder was subjected to particle size andspecific surface area tests, the D50 was 5.6 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 86.15%, the volume cumulative percentage of the particleshaving a particle diameter of 5 μm or less was 53.2%, and the BETspecific surface was 0.58 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material D3 are summarized in Table 1, as shown inTable 1. The index data of the cathode material D3 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2. The test results of the battery performance preparing by powderD3 as the active material of the cathode material are shown in Table 3.

Example 4

Lithium nitrate, aluminum oxide, tungsten oxide and hydroxide (D50: 10.0μm) of nickel-cobalt-manganese precursor having a molar ratio ofNi:Co:Mn=1:1:1 were mixed uniformly at a molar ratio ofLi:Al:W:(Ni+Co+Mn)=1.16:0.003:0.001:0.996 at a rotation speed of 900 rpmfor ball-milling for 20 minutes, and the mixture was put in a mufflefurnace and heated at a rate of 15° C./min to 1000° C. to be sinteredfor 4 hours in an air atmosphere, and cooled to room temperature, andair pre-pulverized at a pressure of 0.2 Mpa and classified by a 300-meshmetal mesh to get lithium ion battery cathode material D4 of sphericalor spherical-like layered structure.

The cathode material D4 powder was tested by the X-ray diffractionpattern, as shown in FIG. 4. The test results showed that full width athalf maximum FWHM (110) of the (110) diffraction peak at diffractionangle 2θ of 64.88 was 0.110, and the structure of the cathode materialwas a single α-NaFeO₂ type layered structure.

The cathode material D4 powder was subjected to a scanning electronmicroscope test, the cathode material D4 powder mainly included primaryparticles of morphology of a spherical or spherical-like and a smallamount of secondary particles agglomerated by primary particles.

The cathode material D4 powder was subjected to particle size andspecific surface area tests, the D50 was 7.0 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 74.2%, the volume cumulative percentage of the particleshaving a particle diameter of 5 μm or less was 35.5%, and the BETspecific surface was 0.40 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material D4 are summarized in Table 1, as shown inTable 1. The index data of the cathode material D4 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2. The test results of the battery performance preparing by powderD4 as the active material of the cathode material are shown in Table 3.

Example 5

1.05 mol of lithium hydroxide monohydrate was dispersed into 720 ml ofmixed aqueous colloid composed of polyethylene glycol having a massconcentration of 3% and acrylamide having a mass concentration of 2%,the mixture was made to be a colloid at a rotation speed of 90 rpm for50 min, and the hydroxide (D50: 8.5 μm) of nickel-cobalt-manganeseprecursor having a molar ratio of Ni:Co:Mn=0.9:0.05:0.05 was added tothe colloid at a molar ratio of Li:(Ni+Co+Mn)=1.05:0.97, and a mixedmaterial was obtained at a rotation speed of 2800 rpm for 45 minutes,and the mixed material was put in a muffle furnace and heated at a rateof 25° C./min to 400° C. to be sintered for 8 hours in an oxygenatmosphere, and cooled to room temperature, and heated at a rate of 25°C./min to 800° C. to be sintered for 20 hours in an oxygen atmosphere,and cooled to room temperature, and air pre-pulverized in an airpressure of 0.3 Mpa to get a cathode material intermediate A oflithium-nickel-cobalt-manganese-oxygen for stand-by. 0.02 mol of cobaltsulfate and 0.01 mol of nickel sulfate were added to 0.5 mol of purewater and the mixture was stirred for 5 min to obtain a solution Bcontaining elements cobalt and manganse for stand-by. The solution B wasadded to the cathode material intermediate A oflithium-nickel-cobalt-manganese and the mixture was stirred for 50 minto obtain a mixture C. The mixture C was put in a muffle furnace andheated in an oxygen atmosphere at a heating rate of 25° C./min to 500°C. to be sintered for 10 hours, and cooled to room temperature, and airpulverized at a pressure of 0.1 MPa, and classified by a 300-mesh metalmesh to obtain a lithium ion battery cathode material D5 of spherical orspherical-like layered structure.

The cathode material D5 powder was tested by the X-ray diffractionpattern, and the test results showed that full width at half maximumFWHM (110) of the (110) diffraction peak at diffraction angle 2θ of64.86 was 0.145, and the structure of the cathode material was a singleα-NaFeO₂ type layered structure.

The cathode material D5 powder was subjected to a scanning electronmicroscope test, the cathode material D5 powder was mainly include theprimary particles of morphology of a spherical or spherical-like and asmall amount of secondary particles agglomerated by primary particles.

The cathode material D5 powder was subjected to particle size andspecific surface area tests, the D50 was 6.2 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 79.37%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 38.7%, and theBET specific surface was 0.62 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material D5 are summarized in Table 1, as shown inTable 1. The index data of the cathode material D5 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2. The test results of the battery performance preparing by powderD5 as the active material of the cathode material are shown in Table 3.

Example 6

1.1 mol of lithium hydroxide monohydrate was dispersed into 800 ml ofmixed aqueous colloid composed of polyethylene glycol having a massconcentration of 1% and an acrylamide having a mass concentration of 4%,the mixture was made to be a colloid at a rotation speed of 100 rpm for30 min, and the hydroxide (D50: 5.5 μm) of nickel-cobalt-manganeseprecursor having a molar ratio of Ni:Co:Mn=8:1:1 was added to thecolloid at a molar ratio of Li:(Ni+Co+Mn)=1.1:0.998, and a mixedmaterial was obtained at a rotation speed of 3000 rpm for 50 minutes,and the mixed material was put in a muffle furnace and heated at a rateof 22° C./min to 550° C. to be sintered for 6 hours in an oxygenatmosphere, and cooled to room temperature, and heated at a rate of 22°C./min to 880° C. to be sintered for 16 hours in an oxygen atmosphere,and cooled to room temperature, and air pre-pulverize in an air pressureof 0.4 Mpa to get cathode material intermediate A oflithium-nickel-cobalt-manganese-oxygen for stand-by. 0.002 mol oftetrabutyl zirconate was added to 0.3 mol of isopropanol and the mixturewas stirred for 30 min to obtain a solution B containing elementzirconium for stand-by. The solution B was added to the cathode materialintermediate A of lithium-nickel-cobalt-manganese and the mixture wasstirred for 60 min to obtain a mixture C. The mixture C was put in amuffle furnace and heated in an oxygen atmosphere at a heating rate of22° C./min to 850° C. to be sintered for 6 hours, and cooled to roomtemperature, and air pulverized at a pressure of 0.4 MPa, and classifiedby a 300-mesh metal mesh to obtain a lithium ion battery cathodematerial D6 of spherical or spherical-like layered structure.

The cathode material D6 powder was tested by the X-ray diffractionpattern, and the test results showed that full width at half maximumFWHM (110) of the (110) diffraction peak at diffraction angle 2θ of64.95 was 0.082, and the structure of the cathode material was a singleα-NaFeO₂ type layered structure.

The cathode material D6 powder was subjected to a scanning electronmicroscope test, the cathode material D6 powder was mainly include theprimary particles of morphology of a spherical or spherical-like and asmall amount of secondary particles agglomerated by primary particles.

The cathode material D6 powder was subjected to particle size andspecific surface area tests, the D50 was 4.0 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 88.5%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 57.5%, and theBET specific surface was 0.71 m²/_(g.)

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material D6 are summarized in Table 1, as shown inTable 1. The index data of the cathode material D6 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2. The test results of the battery performance preparing by powderD6 as the active material of the cathode material are shown in Table 3.

Example 7

Lithium acetate, magnesium oxide, and carboxyl oxide (D50: 12.0 μm) ofnickel-cobalt-manganese precursor having a molar ratio of Ni:Co:Mn=4:3:3were mixed uniformly at a molar ratio ofLi:Mg:(Ni+Co+Mn)=1.15:0.003:0.997 at a rotation speed of 700 rpm forball-milling for 25 minutes, and the mixture was put in a muffle furnaceand heated at a rate of 20° C./min to 900° C. to be sintered for 20hours in an air atmosphere, and cooled to room temperature, and airpre-pulverized at a pressure of 0.6 Mpa and classified by a 300-meshmetal mesh to get lithium ion battery cathode material D7 of sphericalor spherical-like layered structure.

The cathode material D7 powder was tested by the X-ray diffractionpattern, and the test results showed that full width at half maximumFWHM (110) of the (110) diffraction peak at diffraction angle 2θ of64.93 was 0.130, and the structure of the cathode material was a singleα-NaFeO₂ type layered structure.

The cathode material D7 powder was subjected to a scanning electronmicroscope test, the cathode material D4 powder was mainly include theprimary particles of morphology of a spherical or spherical-like and asmall amount of secondary particles agglomerated by primary particles.

The cathode material D7 powder was subjected to particle size andspecific surface area tests, the D50 was 8.0 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 68.5%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 28.3%, and theBET specific surface was 0.30 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material D7 are summarized in Table 1, as shown inTable 1. The index data of the cathode material D7 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and volume basis ofthe particle size of 5 μm or less; D50 and BET) are summarized in Table2. The test results of the battery performance preparing by powder D7 asthe active material of the cathode material are shown in Table 3.

Comparative Example 1

The same process as the preparation method of Example 3 was adopted,which the M source was not added for comparison.

Lithium carbonate and oxide (D50: 7.5 μm) of nickel-cobalt-manganeseprecursor having a molar ratio of Ni:Co:Mn=5:2:3 were mixed uniformly ata molar ratio of Li:(Ni+Co+Mn)=1.2:1 at a rotation speed of 300 rpm forball-milling for 50 minutes, and the mixture was put in a muffle furnaceand heated at a rate of 25° C./min to 800° C. to be sintered for 30hours in an air atmosphere, and cooled to room temperature, and airpulverized at an air pressure of 0.8 Mpa and classified by a 300-meshmetal mesh to get lithium ion battery cathode material El of sphericalor spherical-like layered structure.

The cathode material El powder was tested by the X-ray diffractionpattern, as shown in FIG. 5A. The test results showed that full width athalf maximum FWHM (110) of the (110) diffraction peak at diffractionangle 2θ of 64.87 was 0.070, and the structure of the cathode materialwas a single α-NaFeO₂ type layered structure.

The cathode material E1 powder was subjected to a scanning electronmicroscope test, as shown in FIG. 5B. The cathode material E3 powdermainly included the primary particles of morphology of spherical orspherical-like and a small amount of secondary particles agglomerated byprimary particles.

The cathode material E1 powder was subjected to particle size andspecific surface area tests, the D50 was 5.8 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 81.63%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 49.8%, and theBET specific surface was 0.56 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material E1 are summarized in Table 1, as shown inTable 1. The index data of the cathode material E1 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2. The test results of the battery performance preparing by powderE1 as the active material of the cathode material are shown in Table 3.

Comparative Example 2

The same process as the preparation method of Example 1 was adopted,which the amount of M source was different for comparison.

1.04 mol of lithium hydroxide monohydrate was dispersed into 600 ml ofacrylamide aqueous colloid having a mass concentration of 5%, themixture was made to be a colloid at a rotation speed of 55 rpm for 90min, and the carboxyl oxide (D50: 3μm) of nickel-cobalt-manganeseprecursor having a molar ratio of Ni:Co:Mn=5:2:3 was added to thecolloid at a molar ratio of Li:(Ni+Co+Mn)=1.04:0.94, and a mixedmaterial was obtained at a rotation speed of 2000 rpm for 30 minutes,and the mixed material was put in a muffle furnace and heated at a rateof 15° C./min to 800° C. to be pre-sintered for 4 hours in an airatmosphere, and cooled to room temperature, and heated at a rate of 17°C./min to 980° C. to besintered for 8 hours in an air atmosphere, cooledto room temperature, air pre-pulverized in an air pressure of 1.0 Mpa toget cathode material intermediate A oflithium-nickel-cobalt-manganese-oxygen for stand-by. 0.06 mol oftetrabutyl titanate was added to 0.2 mol of isopropanol and the mixturewas stirred for 10 min to obtain a solution B containing elementtitanium for stand-by. The organic solution B was added to the cathodematerial intermediate A of lithium-nickel-cobalt-manganese and themixture was stirred for 30 min to obtain a mixture C, the mixture C wasput in a muffle furnace and heated in an air atmosphere at a heatingrate of 25° C./min to 500° C. to be sintered for 10 hours, and cooled toroom temperature, and air pulverized at a pressure of 0.1 Mpa, andclassified by a 300-mesh metal mesh to obtain a lithium ion batterycathode material E2 of spherical or spherical-like layered structure.

The cathode material E2 powder was tested by the X-ray diffractionpattern, as shown in FIG. 6A. The test results showed that full width athalf maximum FWHM (110) of the (110) diffraction peak at diffractionangle 2θ of 64.96 was 0.150, the structure of the cathode material andwas a single α-NaFeO₂ type layered structure.

The cathode material E2 powder was subjected to a scanning electronmicroscope test, as shown in FIG. 6B., the cathode material E2 powderwas mainly include the primary particles of a morphology of spherical orspherical-like and a small amount of secondary particles agglomerated byprimary particles.

The cathode material E2 powder was subjected to particle size andspecific surface area tests, the D50 was 3.2 μm, the cumulativepercentage of the number of particles having a particle diameter of 5 μmor less was 92.3%, the cumulative percentage of the volume of theparticles having a particle diameter of 5 μm or less was 62.8%, and theBET specific area was 0.87 m²/g.

The corresponding conditions (sintering temperature, sintering time,airflow pulverizing pressure, M source and product) in the sinteringstep of the cathode material E2 are summarized in Table 1, as shown inTable 1. The index data of the cathode material E2 (the diffractionangle of the (110) plane of the X-ray diffraction, the half-width of thecrystal plane, the cumulative percentages of number and the volume basisof the particle size of 5 μm or less; D50 and BET) are summarized inTable 2, The test results of the battery performance preparing by powderE2 as the active material of the cathode material are shown in Table 3.

TABLE 1 pre- pres- post- sure sin- sin- of post- sin- pres- heat- teringpre- heat- tering method pre- sin- heat- tering post- sure a- ing tem-sin- ing tem- sin- of pul tering ing tem- sin- of mount rate per- teringat- rate per- tering pre- ver- at- rate per- tering pulver- pulver- pro-Ex- M of M ° C./ ature time mos- ° C./ ature time pulver- izing mos- °C./ ature time izing izing duct amples source source min ° C. h pheremin ° C. h izing Mpa phere min ° C. h method Mpa / Example Ti 0.002 15800 4 air 17 980 8 air 1.0 air 15 960 4 air 0.7 D1 1 pulver- pulver-izing izing Example Co/ 0.03/ 18 650 5 oxy- 19 930 12 air 0.5 oxy- 18910 5 air 0.5 D2 2 Mn 0.02 gen pulver- gen pulver- gas zing gas izingExample Y/ 0.001/ / / / air 18 800 30 / / / / / / air 0.8 D3 3 Mg 0.005pulver- izing Example Al/ 0.003/ / / / air 15 1000 4 / / / / / / air 0.2D4 4 W 0.001 pulver- izing Example Co/ 0.02/ 25 400 8 oxy- 25 800 20 air0.3 oxy- 25 500 10 air 0.1 D5 5 Ni 0.01 gen pulver- gen pulver- gas zinggas izing Example Zr 0.002 22 550 6 oxy- 22 880 16 air 0.4 oxy- 22 850 6air 0.4 D6 6 gen pulver- gen pulver- gas zing gas izing Example Mg 0.003/ / / air 20 900 20 / / / / / / air 0.6 D7 7 pulver- izing Compar- / / // / air 25 800 30 / / / / / / air 0.8 E1 ative pulver- Example izing 1Compar- Ti 0.06 15 800 4 air 17 980 8 air 1.0 air 25 500 10 air 0.1 E2ative pulver- pulver- Example zing izing 2

TABLE 2 cumulative cumulative percentage percentage of the of the numberof volume of particles particles having a having a particle particlehalf- diameter of diameter of width 5 μm or 5 μm or D50 BET Examples 2E110 less % less % μ1 m²/g Example 1 64.92 0.073 94.4 63.5 3.0 0.90Example 2 64.89 0.120 91.2 62.3 3.4 0.78 Example 3 64.90 0.098 86.2 53.25.6 0.58 Example 4 64.88 0.110 74.2 35.5 7.0 0.40 Example 5 64.86 0.14579.4 38.7 6.2 0.62 Example 6 64.95 0.082 88.5 57.5 4.0 0.71 Example 764.93 0.130 68.5 28.3 8.0 0.30 Comparative Example 1 64.87 0.070 81.649.8 5.8 0.56 Comparative Example 2 64.96 0.150 92.3 62.8 3.2 0.87

TABLE 3 454261 capacity capacity CR2430 454261 retention retentionCapacity Capacity Capacity Capacity ratio ratio at at at at of 500 of200 4.2- 4.35- 4.2- 4.35- cycles cycles 3.0 V 3.0 V 3.0 V 3.0 V at 4.2 Vat 4.4 V 0.1 C 0.1 C 1.0 C 1.0 C 45° C. 45° C. Example (mAh/g) (mAh/g)(mAh/g) (mAh/g) 1.0C (%) 1.0C (%) Example 1 152 170 150 169 96.8 97.1Example 2 162 175 162 172 93.5 90.2 Example 3 151 168 149 168 97.3 97.8Example 4 149 158 147 160 97.5 98.2 Example 5 194 208 186 202 90.2 89.5Example 6 183 199 179 193 90.8 90.1 Example 7 151 165 150 163 95.8 96.2Comparative Example 1 144 152 146 158 87.3 84.6 Comparative Example 2132 143 136 151 85.2 80.7

According to the above mentioned Examples of the present invention, itcan be seen that the cumulative percentage of the number of particleshaving a particle size of 5 μm or less was between 68.5 and 94.4% of thelithium ion battery cathode material of spherical or spherical-likelayered structure based on primary particles prepared by the invention,that is to say more than 60%, and the cumulative percentage of thevolume of the particles having a particle diameter of 5 μm or less isusually larger than 25% in the volume particle of primary particles andsecondary particles agglomerated by the primary particles of the cathodematerial, and is in the range of 28.3 to 63.5%. After 200 cycles at4.4V, 45° C., 1.0 C, the capacity retention ratio of the batteriesprepared by the cathode material was more than 90%, the maximum capacityretention ratio was even up to 98.2%. After 500 cycles at 4.2V, 45° C.,1.0 C, the capacity retention ratio of the batteries prepared by thecathode material was more than 90%, the maximum capacity retention ratiowas even up to 97.5%; the case of secondary aggregated particlesfragmentation in the process of circulation can be effectively avoided.The material has excellent cycling performance and safety performanceunder high temperature and high voltage, and is suitable for digitalproduct, electric vehicles, electric bicycles, fast charge bus,passenger cars, communications, electricity, energy storage systems.

1. A lithium ion battery cathode material of a spherical orspherical-like layered structure is characterized in that a chemicalformula of said cathode material is Li_(a)Ni_(x)Co_(y)Mn_(z)M_(b)O₂,wherein 1.0≤a≤1.2; 0.0<b≤0.05; 0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50;x+y+z+b=1; M is one or two or more of Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Baand a rare earth element; said lithium ion battery cathode material of aspherical or spherical-like layered structure is prepared by a methodcomprising at least the following steps: dispersing a lithium sourceinto a polyethylene glycol or an acrylamide aqueous colloid to prepare acolloid, and adding nickel-cobalt-manganese precursor according to amolar ratio of Li:(Ni+Co+Mn)=(1.0-1.2):(0.95-1.0) into the colloid toobtain a mixed material, and pre-sintering the mixed material at 400 to800° C. and then sintering at 800 to 980° C., and cooling, andpre-pulverizing and classifying to obtain alithium-nickel-cobalt-manganese-oxygen cathode material intermediate A,adding a solution of M source or a dispersion B into A to obtain amixture C, and post-sintering the mixture C at 500 to 960° C., andcooling, and pulverizing and classifying to obtain a lithium ion batterycathode material of a spherical or spherical-like layered structure. 2.The lithium ion battery cathode material of a spherical orspherical-like layered structure according to claim 1 is characterizedin that a doping amount b of the doping element M is 0.001 to 0.5. 3.The lithium ion battery cathode material of a spherical orspherical-like layered structure according to claim 1 is characterizedin that said cathode material powder comprises primary particles of amorphology of spherical or spherical-like shape and a small amount ofsecondary particles agglomerated by primary particles under scanningelectron microscope (SEM), wherein cumulative percentage of the numberof particles having a particle diameter of 5 μm or less is generallygreater than 60% in the number-basis sizes of primary particles andsecondary particles agglomerated by primary particles of the cathodematerial.
 4. The lithium ion battery cathode material of a spherical orspherical-like layered structure according to claim 2 is characterizedin that a single α-NaFeO₂ type layered structure of said cathodematerial is shown by a powder X-ray diffraction pattern (XRD), and fullwidth at half maximum FWHM (110) of the (110) diffraction peak near adiffraction angle 2θ of 64.9° is 0.073 to 0.145.
 5. The lithium ionbattery cathode material of a spherical or spherical-like layeredstructure according to claim 1 is characterized in that specific surfacearea of said cathode material measured by BET method is 0.3 to 0.9 m²/g.6. The lithium ion battery cathode material of a spherical orspherical-like layered structure according to claim 1 is characterizedin that a median particle diameter of said cathode material is 3.0 to8.0 μm.
 7. A lithium ion battery is characterized by comprising thelithium ion battery cathode material of claim 1 as a positive electrodeactive material.
 8. A lithium ion battery is characterized by comprisingthe lithium ion battery cathode material of claim 3 as a positiveelectrode active material.
 9. The lithium ion battery cathode materialof a spherical or spherical-like layered structure according to claim 1is characterized in that said pre-sintering is carried out for 4 to 8hours, and said sintering is carried out for 8 to 20 hours, and saidpost-sintering is carried out for 4 to 10 hours.
 10. The lithium ionbattery cathode material of a spherical or spherical-like layeredstructure according to claim 1 is characterized in that a pressure ofsaid pre-pulverizing is 0.1 to 1.0 MPa.
 11. The lithium ion batterycathode material of a spherical or spherical-like layered structureaccording to claim 1 is characterized in that a median particle diameterD50 of the nickel-cobalt-manganese precursor is 3 to 12 μm.
 12. Thelithium ion battery cathode material of a spherical or spherical-likelayered structure according to claim 1 is characterized in that the Msource is an oxide of one or two or more selected from the groupconsisting of Mg, Al, Ti, Zr, Y, Co, Ni, Mn, Ba and a rare earthelement, a salt thereof, and an organic compound thereof, acetic acidsalt, sulfate, hydroxyl compound, and ester compound.
 13. A method forpreparing a lithium ion battery cathode material of a spherical orspherical-like layered structure is characterized in that a chemicalformula of said cathode material is Li_(a)Ni_(x)Co_(y)Mn_(z)M_(b)O₂,wherein 1.0≤a≤1.2; 0.0<b<0.05; 0.30≤x≤0.90; 0.05≤y≤0.40; 0.05≤z≤0.50;x+y+z+b=1; M is one or two or more of Mg, Ti, Al, Zr, Y, Co, Mn, Ni, Baand a rare earth element; wherein said method comprises at least thefollowing steps: dispersing a lithium source into a polyethylene glycolor an acrylamide aqueous colloid to prepare a colloid, and addingnickel-cobalt-manganese precursor according to a molar ratio ofLi:(Ni+Co+Mn)=(1.0-1.2):(0.95-1.0) into the colloid to obtain a mixedmaterial, and pre-sintering the mixed material at 400 to 800° C. andthen sintering at 800 to 980° C., and cooling, and pre-pulverizing andclassifying to obtain a lithium-nickel-cobalt-manganese-oxygen cathodematerial intermediate A, adding a solution of M source or a dispersion Binto A to obtain a mixture C, and post-sintering the mixture C at 500 to960° C., and cooling, and pulverizing and classifying to obtain alithium ion battery cathode material of a spherical or spherical-likelayered structure.
 14. The method according to claim 13, which ischaracterized in that said cathode material powder comprises primaryparticles of a morphology of spherical or spherical-like shape and asmall amount of secondary particles agglomerated by primary particlesunder scanning electron microscope (SEM), wherein cumulative percentageof the number of particles having a particle diameter of 5 μm or less isgenerally greater than 60% in the number-basis sizes of primaryparticles and secondary particles agglomerated by primary particles ofthe cathode material.
 15. The method according to claim 13, which ischaracterized in that a doping amount b of the doping element M is 0.001to 0.5.
 16. The method according to claim 13, which is characterized inthat said pre-sintering is carried out for 4 to 8 hours, and saidsintering is carried out for 8 to 20 hours, and said post-sintering iscarried out for 4 to 10 hours.
 17. The method according to claim 13,which is characterized in that a pressure of said pre-pulverizing is 0.1to 1.0 MPa.
 18. The method according to claim 13, which is characterizedin that the lithium source used is one or two or more mixture of lithiumcarbonate, lithium hydroxide monohydrate, lithium nitrate and lithiumacetate.
 19. The method according to claim 13, which is characterized inthat the nickel-cobalt-manganese precursor used is one or more selectedfrom the group consisting of nickel-cobalt-manganese hydroxide,nickel-cobalt-manganese carboxyl oxide, and nickel-cobalt-manganeseoxide.
 20. The method according to claim 13, which is characterized inthat adding the M source comprises one or two or more selected from thegroup consisting mechanical mixing, co-precipitation, andemulsification.